JP7138535B2 - Resin composition and molded product - Google Patents

Description

The present invention relates to resin compositions and molded articles. In particular, the present invention relates to a resin composition using a polycarbonate resin which is excellent in transparency and scratch resistance and which can provide a molded article excellent in surface hardness.

Polycarbonate resins are excellent in mechanical strength, electrical properties, transparency, etc., and are widely used as engineering plastics in various fields such as electric and electronic equipment fields and automobile fields. In recent years, in these fields, there has been progress in thinning, cost reduction, size reduction, and weight reduction of molded products.

For example, Patent Document 1 discloses a graft copolymer (B ) contains 0.1 to 12 parts by mass of a polycarbonate resin composition. The document also describes that the polycarbonate resin composition is excellent in scratch resistance with nails.

Japanese Unexamined Patent Application Publication No. 2017-110180

Conventionally, it has been known that polycarbonate resins containing structural units derived from bisphenol C tend to have high pencil hardness. Here, there is a case where a molded article molded from a polycarbonate resin containing a structural unit derived from bisphenol C is used as a product without being subjected to a treatment such as coating (hereinafter sometimes referred to as "paintless"). However, as a result of investigation by the present inventor, it was found that such a molded article has a slight problem in resistance to scratching by fingernails, although it has a high pencil hardness. Although the resin composition described in Patent Document 1 is a resin composition having excellent resistance to scratching by nails, jet blackness and the like are pursued in the examples of the same document. In other words, development of new materials is required for applications requiring transparency. Fingerprints and the like may be wiped off with a cleaner for non-coating products. Therefore, resistance to nail scratches after wiping off the solvent is also required.
Furthermore, even if a suitable additive is added to the polycarbonate resin to improve the transparency and scratch resistance of the resin composition, the extrudability and transparency may be deteriorated depending on the type of additive.
An object of the present invention is to solve such problems. It is an object of the present invention to provide a resin composition having a high transparency retention ratio and excellent extrudability, and a molded article using the resin composition.

式（１）中、Ｒ¹はメチル基を表し、Ｒ²は水素原子またはメチル基を表し、Ｘ¹は下記のいずれかの式を表し、

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６～１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す。
＜２＞前記（Ｂ）ジエステル化合物が、２価カルボン酸と炭素数１６以上の１価アルコールとから得られるジエステル化合物、または２価アルコールと炭素数１６以上の１価カルボン酸とから得られるジエステル化合物、またはその混合物である、＜１＞に記載の樹脂組成物。
＜３＞前記（Ｂ）ジエステル化合物が、炭素数３～１０の２価カルボン酸と炭素数１６～３０の１価アルコールとから得られるジエステル化合物、または炭素数３～１０の２価アルコールと炭素数２０～４０の１価カルボン酸とから得られるジエステル化合物、またはその混合物である、＜１＞または＜２＞に記載の樹脂組成物。
＜４＞前記（Ａ）ポリカーボネート樹脂は、さらに、下記式（２）で表される構造単位を含む、＜１＞～＜３＞のいずれか１つに記載の樹脂組成物；
式（２）

式（２）中、Ｘ²は下記のいずれかの式を表し、

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６～１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す。
＜５＞前記（Ａ）ポリカーボネート樹脂は、全構造単位中、前記式（１）で表される構造単位を５～９５モル％と、前記式（２）で表される構造単位９５～５モル％を含む、＜４＞に記載の樹脂組成物。
＜６＞厚さ２ｍｍの成形品に成形した時のヘイズが５．０％以下である、＜１＞～＜５＞のいずれか１つに記載の樹脂組成物。
＜７＞＜１＞～＜６＞のいずれか１つに記載の樹脂組成物から形成される成形品。 Based on the above problems, as a result of studies by the present inventors, polycarbonate resins are obtained from a diester compound obtained from a specific polyhydric carboxylic acid and a monohydric alcohol, and / or obtained from a polyhydric alcohol and a monohydric carboxylic acid It has been found that the above problems can be solved by blending a diester compound. Specifically, the above problems have been solved by the following means <1>, preferably by <2> to <7>.
<1> (A) 100 parts by mass of a polycarbonate resin contains 0.3 to 10.0 parts by mass of a diester compound (B), and the (A) polycarbonate resin has the following formula (1) in all structural units: containing 5 mol% or more of the structural unit represented, the diester compound (B) is an ester compound obtained from a polyhydric carboxylic acid and a monohydric alcohol having 16 or more carbon atoms, a polyhydric alcohol and 1 having 16 or more carbon atoms an ester compound obtained from a carboxylic acid, or a mixture of both ester compounds,
resin composition;
formula (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, X ¹ represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group.
<2> The diester compound (B) is a diester compound obtained from a divalent carboxylic acid and a monohydric alcohol having 16 or more carbon atoms, or a diester obtained from a dihydric alcohol and a monovalent carboxylic acid having 16 or more carbon atoms. The resin composition according to <1>, which is a compound or a mixture thereof.
<3> The (B) diester compound is a diester compound obtained from a divalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 16 to 30 carbon atoms, or a dihydric alcohol having 3 to 10 carbon atoms and carbon The resin composition according to <1> or <2>, which is a diester compound obtained from 20 to 40 monovalent carboxylic acids, or a mixture thereof.
<4> The resin composition according to any one of <1> to <3>, wherein the (A) polycarbonate resin further comprises a structural unit represented by the following formula (2);
formula (2)

In formula (2), X ² represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group.
<5> The (A) polycarbonate resin contains 5 to 95 mol% of the structural unit represented by the formula (1) and 95 to 5 mol of the structural unit represented by the formula (2) in all structural units. %, the resin composition according to <4>.
<6> The resin composition according to any one of <1> to <5>, which has a haze of 5.0% or less when molded into a molded article having a thickness of 2 mm.
<7> A molded article formed from the resin composition according to any one of <1> to <6>.

According to the present invention, the surface hardness is high, the scratch resistance and extrudability are excellent, the transparency is high, and the nail scratch resistance is excellent at the initial stage and after wiping off the solvent, and the transparency retention rate is particularly high after the abrasion test. It has become possible to provide a resin composition and a molded article using the resin composition.

The contents of the present invention will be described in detail below. In this specification, the term "~" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit.

The resin composition of the present invention contains 0.3 to 10.0 parts by mass of (B) a diester compound with respect to 100 parts by mass of (A) a polycarbonate resin, and the (A) polycarbonate resin contains, among all structural units, 5 mol% or more of the structural unit represented by the formula (1), and the (B) diester compound is an ester compound obtained from a polycarboxylic acid and a monohydric alcohol having 16 or more carbon atoms, a polyhydric alcohol It is characterized by being an ester compound obtained from a monovalent carboxylic acid having 16 or more carbon atoms, or a mixture of both ester compounds.

With such a configuration, it is possible to provide a resin composition having high surface hardness, excellent extrudability, high transparency, and excellent resistance to scratching by fingernails at the initial stage and after wiping off the solvent. The details of the present invention will be described below.

式（１）中、Ｒ¹はメチル基を表し、Ｒ²は水素原子またはメチル基を表し、Ｘ¹は下記のいずれかの式を表し、

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６～１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す。 <(A) polycarbonate resin>
The (A) polycarbonate resin used in the resin composition of the present invention contains 5 mol % or more of the structural units represented by the formula (1) in all structural units.
formula (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, X ¹ represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group.

Two R ² in formula (1) may be the same or different, and are preferably the same. R ² is preferably a hydrogen atom.

である場合、Ｒ³およびＲ⁴は、少なくとも一方がメチル基であることが好ましく、両方がメチル基であることがより好ましい。
またＸ¹が、

の場合、Ｚは、上記式（１）中の２個のフェニル基と結合する炭素Ｃと結合して、炭素数６～１２の２価の脂環式炭化水素基を形成するが、２価の脂環式炭化水素基としては、例えば、シキロヘキシリデン基、シクロヘプチリデン基、シクロドデシリデン基、アダマンチリデン基、シクロドデシリデン基等のシクロアルキリデン基が挙げられる。置換されたものとしては、これらのメチル置換基、エチル置換基を有するもの等が挙げられる。これらの中でも、シクロヘキシリデン基、シキロヘキシリデン基のメチル置換体（好ましくは３，３，５－トリメチル置換体）、シクロドデシリデン基が好ましい。
式（１）中、Ｘ¹は下記構造が好ましい。

In formula (1), X ¹ is

When , at least one of R ³ and R ⁴ is preferably a methyl group, more preferably both are methyl groups.
Also, if X ¹ is

In the case of, Z is combined with the carbon C that bonds to the two phenyl groups in the above formula (1) to form a divalent alicyclic hydrocarbon group having 6 to 12 carbon atoms, but the divalent Examples of the alicyclic hydrocarbon group include cycloalkylidene groups such as a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, and a cyclododecylidene group. Substituted groups include those having methyl substituents, ethyl substituents, and the like. Among these, a cyclohexylidene group, a methyl-substituted cyclohexylidene group (preferably a 3,3,5-trimethyl-substituted group), and a cyclododecylidene group are preferred.
In formula (1), X ¹ preferably has the following structure.

In the polycarbonate resin (A) in the present invention, the structural unit represented by formula (1) is 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 20 mol% or more, more preferably 40 mol % or more, more preferably 50 mol % or more, even more preferably 60 mol % or more, and even more preferably 65 mol % or more. The upper limit is not limited, but preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, still more preferably 80 mol% or less, more preferably 80 mol% or less, in all structural units. More preferably, it contains 77 mol % or less. Also, the content of the structural unit represented by formula (1) in the polycarbonate resin (A) may be 40 mol % or less in all structural units.

In the present invention, (A) the polycarbonate resin may contain only one type of structural unit represented by formula (1), or may contain two or more types. When two or more kinds are included, it is preferable that the total amount thereof is within the above range.

Specific examples of preferred structural units of formula (1) include the following i) to iv).
i) a structural unit composed of 2,2-bis(3-methyl-4-hydroxyphenyl)propane, ie, R ¹ is a methyl group, R ² is a hydrogen atom, and X ¹ is --C(CH ₃ ) ₂ -- A structural unit that is
ii) a structural unit composed of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, ie R ¹ is a methyl group, R ² is a methyl group and X ¹ is --C(CH ₃ ) ₂ - structural unit,
iii) a structural unit composed of 2,2-bis(3-methyl-4-hydroxyphenyl)cyclohexane, ie a structural unit in which R ¹ is a methyl group, R ² is a hydrogen atom and X ¹ is a cyclohexylidene group ,
iv) a structural unit composed of 2,2-bis(3-methyl-4-hydroxyphenyl)cyclododecane, ie R ¹ is a methyl group, R ² is a hydrogen atom and X ¹ is a cyclododecylidene group It is a structural unit.
Among these, the above i), ii) and iii) are preferred, the above i) and iii) are more preferred, and the above i) is even more preferred.

式（２）中、Ｘ²は下記のいずれかの式を表し、

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６～１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す。
ＺがＣと結合して形成される脂環式炭化水素としては、シクロヘキシリデン基、シクロヘプチリデン基、シクロドデシリデン基、アダマンチリデン基、シクロドデシリデン基等のシクロアルキリデン基が挙げられる。ＺがＣと結合して形成される置換基を有する脂環式炭化水素としては、上述した脂環式炭化水素基のメチル置換体、エチル置換体などが挙げられる。これらの中でも、シクロヘキシリデン基、シクロヘキシリデン基のメチル置換体（好ましくは３，３，５－トリメチル置換体）、シクロドデシリデン基が好ましい。 In the present invention, (A) the polycarbonate resin may have structural units other than the structural unit represented by the formula (1). As another structural unit, a structural unit represented by the following formula (2) is preferable.
formula (2)

In formula (2), X ² represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group.
The alicyclic hydrocarbon formed by combining Z with C includes a cycloalkylidene group such as a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, and a cyclododecylidene group. is mentioned. Examples of the alicyclic hydrocarbon having a substituent formed by combining Z with C include methyl-substituted and ethyl-substituted alicyclic hydrocarbon groups described above. Among these, a cyclohexylidene group, a methyl-substituted cyclohexylidene group (preferably a 3,3,5-trimethyl-substituted group), and a cyclododecylidene group are preferred.

Ｒ³およびＲ⁴は、少なくとも一方がメチル基であることが好ましく、両方がメチル基であることがより好ましい。 The preferred range of X ² in formula (2) is synonymous with the preferred range of X ¹ in formula (1). That is, in formula (2), X ² preferably has the following structure.

At least one of R ³ and R ⁴ is preferably a methyl group, more preferably both are methyl groups.

A preferred specific example of the structural unit represented by the above formula (2) is 2,2-bis(4-hydroxyphenyl)propane, that is, a structural unit composed of bisphenol-A (carbonate structural unit).
In the present invention, the structural unit represented by formula (2) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, and still more preferably 20 mol% of all structural units. More preferably, it contains 23 mol % or more. Further, the structural unit represented by formula (2) may be contained in an amount of 60 mol % or more in all structural units. Further, the structural unit represented by formula (2) preferably contains 95 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, in all structural units, and 60 mol % or less, more preferably 50 mol % or less, even more preferably 40 mol % or less, and even more preferably 35 mol % or less.
In the present invention, (A) polycarbonate resin may not contain structural units represented by formula (2), may contain only one type, or may contain two or more types. When two or more kinds are included, it is preferable that the total amount thereof is within the above range.

In the present invention, (A) the polycarbonate resin may contain a structural unit derived from the dihydroxy compound shown below as another structural unit.

Bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methyl Pentane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3- (1-methylethyl)phenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-(1-methylpropyl)phenyl)propane , 2,2-bis(4-hydroxy-3-cyclohexylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 1,1-bis(4-hydroxyphenyl)decane, 1, 1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4- hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-(1-methylethyl)phenyl)cyclohexane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-(1-methylpropyl)phenyl)cyclohexane, 1,1-bis(4-hydroxy -3-cyclohexylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane, 1,1- Bis(4 - hydroxy-3,5-dimethylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-(1-methylethyl)phenyl)-1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-(1-methylpropyl)phenyl)-1-phenylethane, 1,1-bis( 4-hydroxy-3-cyclohexylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-phenylphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl ) cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclooctane, 4,4′-(1,3-phenylenediisopropylidene)bisphenol, 4,4′-(1,4-phenylenediisopropylidene) bisphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxyphenyl ether, 4 ,4′-dihydroxybiphenyl, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-6-methyl-3-tert-butylphenyl)butane .

Further, as an embodiment of other structural units, structural units represented by formula (1) described in paragraph 0008 of WO2017/099226 are also exemplified, and further, paragraphs 0043 to 0052 of WO2017/099226. The description can also be considered, and the contents thereof are incorporated herein.

式（３）中、Ｒ¹⁵～Ｒ¹⁸は、それぞれ独立に、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～９のアルキル基、炭素数６～１２のアリール基、炭素数１～５のアルコキシ基、炭素数２～５のアルケニル基または炭素数７～１７のアラルキル基を表す；ｎ１、ｎ２およびｎ３は、それぞれ独立に、０～４の整数を表す。
式（３）で表される構造単位の詳細は、特開２０１１－０４６７６９号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Furthermore, as another embodiment of another structural unit, a structural unit represented by the following formula (3) is also exemplified.

In formula (3), R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, represents an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms;
Details of the structural unit represented by formula (3) can be referred to in JP-A-2011-046769, and the contents thereof are incorporated herein.

(A) In the polycarbonate resin, the content of structural units other than the structural units represented by the above formula (1) and the structural units represented by the formula (2) is 30 mol% or less in all structural units. is preferably 20 mol % or less, more preferably 10 mol % or less, and may be 5 mol % or less, or 1 mol % or less.

Preferred embodiments of the (A) polycarbonate resin in the present invention are described below.
(1) A polycarbonate resin containing more than 95 mol % of structural units represented by formula (1) among all structural units.
(2) Among all structural units, 5 to 95 mol% of structural units represented by formula (1) and structural units other than structural units represented by formula (1) (preferably represented by formula (2) Polycarbonate resin containing 95 to 5 mol% or more of the
When the polycarbonate resin used in the present invention contains a structural unit other than the structural unit represented by formula (1) (preferably a structural unit represented by formula (2)), the following blend forms are exemplified.
A polycarbonate resin (A1) in which more than 50 mol% (preferably 70 mol% or more, 95 mol% or more) of all structural units are structural units represented by formula (1), and 95 mol% of all structural units A mixture of polycarbonate resin (A2) consisting of a structural unit represented by formula (2):
Copolycarbonate resin (A3) in which the total of structural units represented by formula (1) and structural units represented by formula (2) accounts for more than 95 mol% of all structural units:
- A mixture of the polycarbonate resin (A1), the polycarbonate resin (A2), and the copolymerized polycarbonate resin (A3):
- A mixture of the polycarbonate resin (A1) and the copolymerized polycarbonate resin (A3);
- A mixture of the copolymerized polycarbonate resin (A3) and the polycarbonate resin (A2);
- In any of the above embodiments, a mixture containing two or more of at least one of the polycarbonate resin (A1), the polycarbonate resin (A2) and the copolymerized polycarbonate resin (A3);
In any embodiment, it is sufficient that the structural unit represented by formula (1) in (A) the polycarbonate resin is contained at a rate of 5 mol% or more, and furthermore, the structure represented by formula (1) It is preferable that the unit and the structural unit represented by formula (2) are contained in the total structural units in a proportion that satisfies the preferred range described above.

In the present invention, among the blend forms exemplified above, a form containing (A1) a polycarbonate resin and (A2) a polycarbonate resin is particularly preferred. When (A1) polycarbonate resin and (A2) polycarbonate resin are included, the mixing ratio of the two is preferably 5:95 to 95:5, more preferably 10:90 to 95:5, in terms of mass ratio. more preferably 15:85 to 95:5, even more preferably 15:85 to 90:10, even more preferably 50:50 to 90:10, even more preferably 60:40 to 85 :15 is even more preferred, 65:35 to 85:15 is particularly preferred, 60:40 to 80:20 is even more preferred, and 70:30 to 80:20 is even more preferred. may
The resin composition of the present invention may contain only one kind of (A1) polycarbonate resin and (A2) polycarbonate resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range. By setting it as such a structure, pencil hardness can be made high.

In the present invention, the lower limit of the viscosity-average molecular weight (Mv) of the polycarbonate resin (A) is preferably 9,000 or more, more preferably 10,000 or more, and more preferably 12,000 or more. More preferred. Also, the upper limit of Mv is preferably 32,000 or less, more preferably 30,000 or less, and even more preferably 28,000 or less.
By setting the viscosity-average molecular weight to the above lower limit or more, moldability is improved and a molded product having high mechanical strength can be obtained. Further, by setting the content to the above upper limit or less, the fluidity of the molded product is improved, and thin molded products can be efficiently produced.
The viscosity-average molecular weight (Mv) is measured according to the method described in the examples below (the same applies to Mv hereinafter). When two or more types of (A) polycarbonate resins are included, the sum of the values obtained by multiplying the viscosity-average molecular weight of each polycarbonate resin by the mass fraction is used. Hereinafter, the viscosity average molecular weight will be similarly considered.

The (A) polycarbonate resin has a pencil hardness measured according to ISO 15184 of 3B to 2H, preferably B to 2H, more preferably HB to 2H, and H or 2H. is more preferred, and 2H is even more preferred. The pencil hardness is measured according to the method described in the examples below (the same applies to the pencil hardness below). When two or more types of (A) polycarbonate resins are included, the pencil hardness of the mixture is preferably within the above range.

The method for producing the (A) polycarbonate resin is not particularly limited, and any known method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid-phase transesterification method of a prepolymer. Among these, the interfacial polymerization method and the melt transesterification method are preferred.

The resin composition of the present invention preferably contains (A) a polycarbonate resin in a proportion of 80% by mass or more of the composition, more preferably 85% by mass or more, and more preferably 90% by mass or more. More preferably, it is contained at a rate of 93% by mass or more. (A) Although the upper limit of the polycarbonate resin is not particularly defined, it can be, for example, 99.4% by mass or less.
The resin composition of the present invention may contain only one type of (A) polycarbonate resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<(B) Diester compound>
The resin composition of the present invention contains (B) a diester compound.
The (B) diester compound used in the present invention is an ester compound obtained from a polyhydric carboxylic acid and a monohydric alcohol having 16 or more carbon atoms (preferably a monohydric alcohol having 16 to 50 carbon atoms), a polyhydric alcohol and a carbon number It is an ester compound obtained from 16 or more monovalent carboxylic acids (preferably monovalent carboxylic acids having 16 to 50 carbon atoms), or a mixture of both.
By containing such a (B) diester compound in the resin composition of the present invention, the decomposition of the polycarbonate resin is suppressed, the generation of gas during molding can be effectively suppressed, and compatibility with the polycarbonate resin is improved. Excellent for Therefore, it is possible to obtain a resin composition capable of forming a molded article having excellent extrudability, high transparency, and excellent resistance to fingernail scratches at the initial stage and after wiping off the solvent.

The diester compound (B) is preferably a diester compound comprising a divalent carboxylic acid and a monohydric alcohol, a diester compound comprising a monovalent carboxylic acid and a dihydric alcohol, or a mixture thereof. The monohydric carboxylic acid and the monohydric alcohol may each contain an aliphatic structure, an alicyclic structure and/or an aromatic structure, and each contain an aliphatic structure and/or an alicyclic structure. is preferred. The monohydric carboxylic acid and the monohydric alcohol preferably comprise a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group, respectively.
The monohydric alcohol and monocarboxylic acid each have 16 or more carbon atoms, and may also have 18 or more carbon atoms or 20 or more carbon atoms. The upper limit of the number of carbon atoms in each of the monohydric alcohol and monocarboxylic acid is preferably 50 or less, more preferably 40 or less, still more preferably 32 or less, even more preferably 30 or less, and may be 28 or less.
The dihydric carboxylic acid and the dihydric alcohol may each contain an aliphatic structure, an alicyclic structure and/or an aromatic structure, and each contain an aliphatic structure and/or an alicyclic structure. is preferred.
The dihydric carboxylic acid and the dihydric alcohol preferably comprise a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group, respectively. The number of carbon atoms in each of the dihydric carboxylic acid and the dihydric alcohol is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and even more preferably 6 or more. preferable. The number of carbon atoms in each of the dihydric carboxylic acid and the dihydric alcohol is preferably 10 or less, more preferably 8 or less.

In particular, the diester compound used in the present invention is a diester compound obtained from a divalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 16 to 40 carbon atoms, or a dihydric alcohol having 3 to 10 carbon atoms and a carbon number. It is preferably a diester compound obtained from a monovalent carboxylic acid having 16 to 40 carbon atoms, or a mixture thereof, and a diester obtained from a divalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 16 to 30 carbon atoms. compound, or a diester compound obtained from a dihydric alcohol having 3 to 10 carbon atoms and a monovalent carboxylic acid having 16 to 30 carbon atoms, or a mixture thereof, and a divalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 16 to 30 carbon atoms or a mixture thereof.
Furthermore, in the diester compound composed of a divalent carboxylic acid and a monohydric alcohol used in the present invention, the number of carbon atoms in the monohydric alcohol is greater than the number of carbon atoms in the divalent carboxylic acid by 10 or more, preferably 10 to 20. is more preferable. Alternatively, in the diester compound composed of a monovalent carboxylic acid and a dihydric alcohol used in the present invention, the number of carbon atoms in the dihydric alcohol is preferably 10 or more larger than the number of carbon atoms in the monovalent carboxylic acid, preferably 10 to 20 larger. is more preferable. By adopting such a structure, gas is less likely to be generated during extrusion or molding, and the appearance and physical properties of the molded product tend to be further improved.

Specific examples of monovalent carboxylic acids (number of carbon atoms in parentheses) include behenic acid (22), lignocericic acid (24), cerotic acid (26), montanic acid (28), and melissic acid (30). be done.

Specific examples of monohydric alcohols (number of carbon atoms in parentheses) include stearyl alcohol (18), behenyl alcohol (22) and montanyl alcohol (28).

Specific examples of divalent carboxylic acids (number of carbon atoms in parentheses) include oxalic acid (2), malonic acid (3), succinic acid (4), glutaric acid (5), adipic acid (6), pimelic acid ( 7), suberic acid (8), azelaic acid (9), sebacic acid (10), phthalic acid (8), isophthalic acid (8), terephthalic acid (8), 1,4-cyclohexanedicarboxylic acid (8), 1,3-cyclohexanedicarboxylic acid (8), 1,2-cyclohexanedicarboxylic acid (8) and the like.

Specific examples of dihydric alcohols (number of carbon atoms in parentheses) include ethylene glycol (2), propylene glycol (3), tetramethylene glycol (4), diethylene glycol (4), and 1,4-benzenedimethanol (8). , 1,4-cyclohexanedimethanol (8) and the like.

The hydroxyl value of the diester compound (B) is preferably 100 mgKOH/g or less, more preferably 70 mgKOH/g or less, even more preferably 50 mgKOH/g or less, and 10 mgKOH/g or less. is more preferred. Although the lower limit of the hydroxyl value of the diester compound (B) is not particularly defined, it is, for example, 1 mgKOH/g or more. (B) By setting the hydroxyl value of the diester compound to 100 mgKOH/g or less, it is possible to effectively suppress the acceleration of the decomposition of the polycarbonate resin, making it difficult for gas to be generated during extrusion or molding, and improving the appearance of the molded product. Physical properties tend to improve, which is preferable.
According to this aspect, the molded article obtained from the composition of the present invention is also excellent in resistance to nail scratches after wiping with cotton impregnated with ethanol.

The molecular weight of the diester compound (B) used in the present invention is preferably 2000 or less, more preferably 1800 or less, even more preferably 1400 or less, even more preferably 1000 or less, and 900 or less. is even more preferable. The lower limit is preferably 200 or more, more preferably 500 or more. When the molecular weight of the diester compound (B) is within the above range, a molded article having an excellent balance between high transparency and high scratch resistance can be obtained. When the (B) ester compound is a mixture, the number average molecular weight is used.

The diester compound used in the present invention is often a mixture of a plurality of compounds with different carbon numbers, but in the present invention, the main component (preferably 50% by mass or more, more preferably 70% by mass or more) contains It refers to an ester compound.

The resin composition of the present invention contains 0.3 to 10.0 parts by mass of (B) diester compound per 100 parts by mass of (A) polycarbonate resin. (B) The lower limit of the amount of the diester compound is preferably 0.4 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin (A). It is more preferably 0.6 parts by mass or more, still more preferably 0.8 parts by mass or more, even more preferably 1.0 parts by mass or more, and further preferably 1.5 parts by mass or more. It is more preferably 1.8 parts by mass or more, particularly preferably 1.8 parts by mass or more, and may be 2.0 parts by mass or more, more than 2.0 parts by mass, or 2.2 parts by mass or more. By setting it as the said range, resistance to a nail damage can be improved more. The upper limit of the amount of the diester compound (B) is preferably 9.0 parts by mass or less, 8.0 parts by mass or less, 7.0 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). It may be 6.0 parts by mass or less, 5.5 parts by mass or less, 4.0 parts by mass or less, 3.5 parts by mass or less, or 2.5 parts by mass or less. By setting it within the preferable range, hydrolysis resistance is improved, and mold contamination can be more effectively suppressed. In the present invention, even if the blending amount of (B) the diester compound is small, it is possible to obtain a structure having excellent nail scratch resistance. The resin composition of the present invention may contain only one type of (B) diester compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Other ingredients>
The resin composition of the present invention may optionally contain other components than those mentioned above, as long as the desired physical properties are not significantly impaired. Examples of other components include thermoplastic resins other than the polycarbonate resins described above (for example, acrylic resins, etc.), various resin additives, and the like.
Although the resin composition of the present invention preferably contains no inorganic filler, it may contain an inorganic filler. By including the inorganic filler, the mechanical strength of the resulting molded article can be further improved. As an embodiment of the resin composition of the present invention, it does not contain an inorganic filler, or 8 parts by mass or less (preferably 6 parts by mass or less, more preferably 6 parts by mass or less) of an inorganic filler with respect to 100 parts by mass of the (A) polycarbonate resin. is 4 parts by mass or less, more preferably 1 part by mass or less). The transparency of the obtained molded article can be further improved by not including the inorganic filler or by setting the blending amount within the above range. As the inorganic filler, the descriptions in paragraphs 0075 to 0079 of JP-A-2017-110180 can be referred to, and the contents thereof are incorporated herein.
Examples of resin additives include stabilizers (heat stabilizers, antioxidants, etc.), ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, dyes, pigments, antifog agents, lubricants, antiblocking agents. , fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. One resin additive may be contained, or two or more resin additives may be contained in any combination and ratio.
The resin composition of the present invention can be configured to substantially contain no release agent other than the diester compound (B). “Substantially free” means that the amount of the other release agent is less than 0.5 parts by mass, preferably 0.3 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). It is more preferably 0.1 parts by mass or less, further preferably 0.01 parts by mass or less, even more preferably 0.001 parts by mass or less, and more preferably 0.0001 parts by mass or less. More preferred.

式（Ｘ）中、Ｒ⁶、Ｒ⁷およびＲ⁸は、それぞれ独立に、水素原子または炭素数１～２０の炭化水素基を表し、Ｒ⁹は置換基を有していてもよい炭素数６～２０の芳香族炭化水素基、または、置換基を有していてもよい炭素数６～１７の芳香族炭化水素基で置換された炭素数１～３の脂肪族炭化水素基を表す。 <<Acrylic Resin>>
The polycarbonate resin composition of the present invention may contain an acrylic resin as a thermoplastic resin other than the polycarbonate resin. The acrylic resin is preferably an acrylic resin having a structural unit represented by formula (X) below.
Formula (X)

In formula (X), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ is optionally substituted C 6 represents an aromatic hydrocarbon group of up to 20 or an aliphatic hydrocarbon group of 1 to 3 carbon atoms substituted with an optionally substituted aromatic hydrocarbon group of 6 to 17 carbon atoms.

In addition to the above, the acrylic resin used in the present invention can employ those described in WO2014/038500, WO2013/094898, JP-A-2006-199774, and JP-A-2010-116501. , the contents of which are incorporated herein.
When the acrylic resin is blended, the blending amount is preferably in the range of 1 to 30% by mass, more preferably in the range of 1 to 10% by mass of the polycarbonate resin composition of the present invention.

<<Stabilizer>>
Stabilizers include heat stabilizers and antioxidants.
Phosphorus-based stabilizers are preferably used as heat stabilizers.
Any known phosphorus stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acid pyrophosphate metal salts such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of group 1 or group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, zinc phosphate; is particularly preferred.

Examples of organic phosphite compounds include triphenylphosphite, tris(monononylphenyl)phosphite, tris(monononyl/dinonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, monooctyl Diphenylphosphite, dioctylmonophenylphosphite, monodecyldiphenylphosphite, didecylmonophenylphosphite, tridecylphosphite, trilaurylphosphite, tristearylphosphite, 2,2-methylenebis(4,6-di- tert-butylphenyl)octyl phosphite and the like.
Specific examples of such organic phosphite compounds include, for example, "ADEKA STAB (registered trademark; hereinafter the same) 1178", "ADEKA STAB 2112", and "ADEKA STAB HP-10" manufactured by Johoku Chemical Industry Co., Ltd. "JP-351", "JP-360", "JP-3CP", BASF's "Irgafos (registered trademark; hereinafter the same) 168", and the like.

As the antioxidant, a hindered phenol stabilizer is preferably used.
Specific examples of hindered phenol stabilizers include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-(3,5-di-tert- Butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl )-4-hydroxyphenyl]methyl]phosphate, 3,3′,3″,5,5′,5″-hexa-tert-butyl-a,a′,a″-(mesitylene-2,4 ,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl ) propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy benzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1, 3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate and the like. be done.

Among them, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate preferable. Specific examples of such hindered phenol-based stabilizers include, for example, "Irganox (registered trademark; hereinafter the same) 1010" and "Irganox 1076" manufactured by BASF, "ADEKA STAB AO-50" and "ADEKA STAB AO-60” and the like.

The content of the stabilizer in the resin composition of the present invention is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin. Also, it is usually 1 part by mass or less, preferably 0.5 parts by mass or less, and more preferably 0.3 parts by mass or less. By setting the content of the stabilizer within the above range, the effect of addition of the stabilizer is exhibited more effectively.

<<Ultraviolet absorber>>
As for the ultraviolet absorber, the descriptions in paragraphs 0059 to 0062 of JP-A-2016-216534 can be referred to, and the contents thereof are incorporated herein.

<<Antistatic agent>>
As the antistatic agent, the descriptions in paragraphs 0063 to 0067 of JP-A-2016-216534 can be referred to, and the contents thereof are incorporated herein.

<<flame retardant>>
As the flame retardant, the descriptions in paragraphs 0068 to 0075 of JP-A-2016-216534 can be referred to, and the contents thereof are incorporated herein.

<Characteristics of resin composition>
The resin composition of the present invention can achieve low haze. For example, the haze of a molded product obtained by molding the resin composition of the present invention to a thickness of 2 mm can be 5.0% or less, further 3.0% or less, 2.0% or less, or 1.0% or less. , 0.5% or less, or 0.4% or less. The lower limit of haze is ideally 0%, but 0.01% or more, or even 0.07% or more is also a practical level. The method for measuring haze follows the description in Examples described later.

A test piece having a thickness of 2 mm (preferably a test piece having a length of 150 mm, a width of 100 mm, and a thickness of 2 mm) formed from the resin composition of the present invention was subjected to initial reciprocating abrasion using bleaching (100% cotton, 20 × 20 count). ΔHaze, which is the difference in haze before and after the test, is preferably 5.00% or less, more preferably 4.00% or less, even more preferably 3.00 or less, and 2.00% or less. is more preferably 1.50% or less. The lower limit of the haze before and after the initial reciprocating abrasion test is ideally 0%, but 0.01% or more, or even 0.07% or more is a practical level. The method for measuring Δhaze before and after the initial reciprocating abrasion test follows the description of Examples described later.

A test piece having a thickness of 2 mm (preferably a test piece having a length of 150 mm × width of 100 mm × thickness of 2 mm) formed from the resin composition of the present invention, the value of Δhaze before and after the reciprocating abrasion test after wiping off the solvent, and the above initial The difference in Δhaze values before and after the reciprocating abrasion test (Δhaze before and after the reciprocating abrasion test after wiping off the solvent - Δhaze before and after the initial reciprocating abrasion test) is preferably 2.0 or less, and 1.5 or less. It is more preferably 1.2 or less, even more preferably 1.0 or less, and even more preferably 0.9 or less. The lower limit of Δhaze before and after the reciprocating abrasion test after wiping off the solvent - Δhaze before and after the initial reciprocating abrasion test is ideally 0%, but 0.01% or more, even 0.07% or more is a practical level. is.
The Δhaze before and after the reciprocating abrasion test after wiping off the solvent−the Δhaze before and after the initial reciprocating abrasion test follows the description in Examples described later.

<Method for producing resin composition>
The method for producing the resin composition of the present invention is not limited, and a wide range of known methods for producing a polycarbonate resin composition can be employed. After pre-mixing using various mixers such as a tumbler and Henschel mixer, a method of melt-kneading with a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader can be mentioned.
The melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320°C.

<Molded product>
The resin composition (for example, pellets) described above is molded by various molding methods to obtain molded articles. That is, the molded article of the present invention is molded from the resin composition of the present invention.
The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. , odd-shaped products, hollow products, frame-shaped products, box-shaped products, panel-shaped products, button-shaped products, and the like. Among them, film-shaped, frame-shaped, panel-shaped, and button-shaped ones are preferable, and the thickness of the frame-shaped and panel-shaped ones is, for example, about 1 mm to 5 mm.

The method for molding the molded article is not particularly limited, and conventionally known molding methods can be employed, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, Gas-assisted blow molding method, blow molding method, extrusion blow molding method, IMC (in-mold coating molding) method, rotational molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method , pressure molding, and the like. In particular, the resin composition of the present invention is suitable for moldings obtained by injection molding, injection compression molding, and extrusion molding. However, it goes without saying that the resin composition of the present invention is not limited to the molded articles obtained therefrom.

The molded article of the present invention is suitably used for parts such as electrical and electronic equipment, OA equipment, personal digital assistants, machine parts, household appliances, vehicle parts, various containers, lighting equipment and the like. Among these, it is particularly used for electrical and electronic equipment, OA equipment, information terminal equipment and housings of home appliances, lighting equipment and vehicle parts (especially vehicle interior parts), with vehicle interior parts being particularly preferred.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

1. Raw materials <Production Example 1: Production of polycarbonate resin A1>
26.14 mol (6.75 kg) of bisphenol C (BPC) and 26.79 mol (5.74 kg) of diphenyl carbonate were placed in a SUS reactor (inner volume: 10 liters) equipped with a stirrer and a distillate condenser. After the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 220° C. over 30 minutes under a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) as a transesterification reaction catalyst is added to the molten reaction solution in an amount of 1.5×10 ⁻⁶ mol per 1 mol of BPC. In addition, the reaction solution was stirred and brewed at 220° C. for 30 minutes in a nitrogen gas atmosphere. Next, at the same temperature, the pressure inside the reactor was reduced to 100 Torr over 40 minutes, and the reaction was continued for 100 minutes to distill off phenol.
Next, the temperature in the reactor was raised to 284° C. over 60 minutes and the pressure was reduced to 3 Torr to distill almost the entire theoretical amount of phenol. Next, the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was continued for an additional 60 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rpm, the temperature of the reaction liquid immediately before the reaction was completed was 289° C., and the stirring power was 1.00 kW.
Next, the reaction liquid in a molten state is fed into a twin-screw extruder, and butyl p-toluenesulfonate in an amount four times the molar amount of cesium carbonate is fed from the first feed port of the twin-screw extruder, After kneading with the reaction liquid, the reaction liquid was extruded through a die of a twin-screw extruder into strands and cut with a cutter to obtain pellets of polycarbonate resin A1.

<Production Example 2: Synthesis of dibehenyl adipate>
Diethyl adipate (manufactured by Tokyo Chemical Industry Co., Ltd., 40.0 g), behenyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., 129 g) and 5 mass% toluene solution of tetrabutyl orthotitanate (manufactured by Tokyo Chemical Industry Co., Ltd.) ( 2.64 mL) were mixed, and the mixture was heated at 220° C. for 3 hours under a nitrogen atmosphere, then under reduced pressure to 6 kPa and heated at 220° C. for 2 hours to react while distilling off the produced ethanol. After the reaction, dilute with toluene (300 mL), wash with 1% by mass aqueous solution (150 g) of disodium hydrogen citrate 1.5 hydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and then water (150 g). was washed twice with The obtained oil layer was filtered through celite to remove residual insoluble matter, and then the solvent was distilled off under reduced pressure. A solution of chloroform (300 mL) and toluene (150 mL) was added to the residue for recrystallization, and the residual solvent was evaporated under reduced pressure to give dibehenyl adipate (130 g) as a white powder.

<Production Example 3: Synthesis of dibehenyl 1,4-cyclohexanedicarboxylate>
5 of dimethyl 1,4-cyclohexanedicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd., 40.0 g), behenyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., 131 g) and tetrabutyl orthotitanate (manufactured by Tokyo Chemical Industry Co., Ltd.) A mass% toluene solution (2.60 mL) was mixed, and the mixture was heated at 220°C for 3 hours under a nitrogen atmosphere, then under reduced pressure to 6 kPa and heated at 220°C for 2 hours to react while distilling off the generated methanol. After the reaction, dilute with toluene (280 mL), wash with a 1% by mass aqueous solution (140 g) of disodium hydrogen citrate 1.5 hydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and then water (140 g). was washed twice with The obtained oil layer was filtered through celite to remove residual insoluble matter, and then the solvent was distilled off under reduced pressure. A solution of acetone (480 mL) and toluene (160 mL) was added to the residue for recrystallization, and the residual solvent was evaporated under reduced pressure to give dibehenyl 1,4-cyclohexanedicarboxylate (136 g) as a white powder.

Materials shown in Table 1 below were used for the production of the resin composition of the present invention.

<Measurement of viscosity average molecular weight (Mv) of polycarbonate resin>
The viscosity-average molecular weight (Mv) of the polycarbonate resin is obtained by using methylene chloride as a solvent and using an Ubbelohde viscometer to determine the intrinsic viscosity (η) (unit: dL / g) at a temperature of 20 ° C., and the following Schnell viscosity Calculated from the formula.
η=1.23×10 ⁻⁴ Mv ^0.83

<Measurement of pencil hardness of polycarbonate resin>
After drying the polycarbonate resin pellets at 100 ° C. for 5 hours, using an injection molding machine (“α-2000i-150B” manufactured by Fanuc Co., Ltd.), the cylinder setting temperature is 260 ° C., the mold temperature is 70 ° C., and the screw rotation speed is 100 rpm. A flat test piece (150 mm×100 mm×2 mm thick) was prepared under the conditions of an injection speed of 30 mm/sec. With respect to this flat test piece, the pencil hardness measured with a load of 750 g was obtained using a pencil hardness tester according to ISO 15184.
A pencil hardness tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.

<Measurement of hydroxyl value of diester compounds and their substitutes>
The hydroxyl value is the mg number of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1 g of the sample is acetylated. Sometimes it is an indicator of the number of hydroxyl groups left unreacted.
The hydroxyl value was measured according to the method specified in JIS K 0070.

2. Examples 1 to 6, Comparative Examples 1 to 21
<Production of resin composition pellets>
Each component described in Table 1 above was blended in the proportions shown in Tables 2 to 4 below (all expressed in parts by mass), uniformly mixed in a tumbler mixer, and then ) Using TEX30α manufactured by Japan Steel Works, feed the extruder from the barrel upstream of the extruder at a cylinder setting temperature of 260 ° C., a screw rotation speed of 180 rpm, and a discharge rate of 30 kg / hr, and melt and knead to form resin composition pellets. (However, for Comparative Example 11, extrusion was not possible).

<Mole ratio of polycarbonate resin>
The molar ratio (mol%) in Tables 2 to 4 described later is an index showing the content of the structural unit represented by formula (1) in the polycarbonate resin contained in the resin composition, and the mixture of the resins used. It was calculated from the viscosity average molecular weight using the ratio and the molecular weight of the structural unit represented by formula (1).

<Possibility of Extrusion>
In the production of the resin composition pellets, whether or not extrusion was possible was visually confirmed and evaluated as follows.
a: extrudable b: extrusion unstable c: extrudable (polycarbonate resin decomposes)

<Amount of extrusion gas generated>
In the production of the above resin composition pellets, the amount of gas generated in Comparative Example 2 was used as a standard, and when the amount of gas generated was equal to or less than that, it was evaluated as the standard amount of gas generation (a), and the extrusion was compared with the standard amount. The amount of gas generated was visually evaluated as follows.
a: gas generation standard b: slightly high c: high

<Comprehensive evaluation of extrudability>
Evaluation was made as follows based on the results of whether or not extrusion was possible and the amount of gas generated.
A: Both extrudability and gas generation rate are a.
B: Other than A above and C below.
C: At least one of whether or not extrusion is possible and the amount of gas generated is c.

<Production of test piece for evaluation as molded body>
After drying the resin composition pellets obtained above at 100 ° C. for 5 hours, an injection molding machine (“α-2000i-150B” manufactured by Fanuc Corporation) was used to set the cylinder temperature to 260 ° C., the mold temperature to 70 ° C., A flat test piece of 150 mm×100 mm×2 mm thickness was injection molded under conditions of a screw rotation speed of 100 rpm and an injection speed of 30 mm/sec.
In the table, "cannot be molded" means that the test piece for evaluation could not be molded because extrusion was impossible or extremely unstable.

<Measurement of Pencil Hardness of Resin Composition>
For the flat test piece obtained above, the pencil hardness measured under a load of 1 kg was determined using a pencil hardness tester according to ISO 15184.
A pencil hardness tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.

<Measurement of haze>
The haze (unit: %) of the flat test piece obtained above was measured using a haze meter.
As the haze meter, NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. was used.

<Coefficient of dynamic friction (30N)>
For the flat test piece obtained above, in accordance with ISO 19252, a scratch tester is used with a spherical terminal of 1 mmφ, the test speed is 100 mm / sec, the vertical load is variable from 1 N to 50 N during the test distance of 100 mm. A horizontal load and a vertical load were measured at a load of 30 N, and a dynamic friction coefficient (horizontal load/vertical load) was obtained. A smaller coefficient of dynamic friction is preferable.
A scratch tester manufactured by Kato Tech Co., Ltd. was used.

<Initial nail scratch resistance>
Sensory evaluation was performed by rubbing the flat test piece obtained above 10 times with a fingernail.
a: No scratches and good slipperiness.
b: Slightly scratched, but slippery.
c: Scratches less than d, but still damaged.
d: hurt.

<Resistance to nail scratches after wiping off solvent>
The surface of the flat test piece obtained above was wiped with a cotton pad impregnated with ethanol, and sensory evaluation was performed in the same manner as for the nail scratch resistance.

<Δhaze before and after the initial reciprocating wear test>
The haze of the flat test piece obtained above was measured in the same manner as described above (the haze at this time is referred to as haze a).
On the other hand, for the same flat test piece obtained above, using a flat abrasion tester, bleached cloth (100% cotton, 20 × 20 count cut to 15 cm × 33 cm) was folded 18 times, and flat abrasion was performed. It was attached to a jig of a testing machine, and tested with a reciprocating cycle of 40 times/min, a load of 1 kg, and a reciprocating number of 500 times. After the reciprocating abrasion test, the haze of the flat test piece was measured in the same manner as described above (the haze at this time is referred to as haze b). "Haze b - haze a" was defined as Δhaze before and after the initial reciprocating abrasion test.
The surface abrasion tester was manufactured by Daiei Kagaku Seiki Seisakusho.
The bleaching used was bleached from Nankai Co., Ltd.

<Δhaze before and after reciprocating abrasion test after wiping off solvent - Δhaze before and after initial reciprocating abrasion test>
After wiping the surface of the flat test piece obtained above with gauze impregnated with ethanol, the haze was measured in the same manner as described above (the haze at this time is referred to as haze c).
Then, in the same manner as described above, using a flat abrasion tester, the bleached cloth (100% cotton, 20 × 20 count cut into 15 cm × 33 cm) was folded 18 times, attached to the jig of the flat abrasion tester, and reciprocated. The test was performed with a cycle of 40 times/min, a load of 1 kg, and a reciprocation number of 500 times. The flat test piece after the reciprocating abrasion test was measured for haze in the same manner as described above (the haze at this time is defined as haze d). "Haze d - haze c - Δhaze before and after the initial reciprocating abrasion test" was defined as "Δhaze before and after the reciprocating abrasion test after wiping off the solvent - Δhaze before and after the initial reciprocating abrasion test".
The surface abrasion tester was manufactured by Daiei Kagaku Seiki Seisakusho.
The bleaching used was bleached from Nankai Co., Ltd.

<Comprehensive evaluation (extrudability, haze, scratch resistance)>
A comprehensive evaluation was made based on extrudability, haze, and scratch resistance.
1: Extrusion comprehensive evaluation is A, haze is 5.0% or less, and nail scratch resistance (initial) and nail scratch resistance after solvent wiping are a.
2: Other than 1 above and 3 below.
3: Satisfy one or more of the following.
The extrudability comprehensive evaluation is C.
Haze is greater than 5.0%.
Nail scratch resistance is c or d.
The nail scratch resistance after wiping off the solvent is c or d.

The results are shown in Tables 2 to 4 below.

In the above table, the "proportion of formula (1)" is the proportion (mol%) of the structural unit represented by formula (1) among all the structural units constituting the polycarbonate resin.
As is clear from the above results, the resin composition of the present invention had high surface hardness, excellent extrudability, low haze, and excellent nail scratch resistance at the initial stage and after wiping off the solvent (Example 1 to Example 6). Furthermore, the Δhaze before and after the initial reciprocating abrasion test, and the difference between the Δhaze before and after the reciprocating abrasion test after wiping off the solvent and the Δhaze before and after the initial reciprocating abrasion test tended to be small.
On the other hand, when the structural unit represented by formula (1) was not included (Comparative Examples 1, 19, 20 and 21), any one of the above performances was inferior. Specifically, the scratch resistance was poor initially and after wiping off the solvent, the haze was high, the extrudability was poor, and the Δhaze before and after the initial reciprocating abrasion test was high.
In addition, when only ester compounds other than the diester compounds defined in the claims of the present invention and their substitutes (B4 to B10 above) were blended (Comparative Examples 1 to 12, 19, 20), the extrudability was inferior. , the haze tended to be high, and the scratch resistance at the initial stage and after wiping off the solvent tended to be poor.
In addition, even if the diester compound defined in the claims of the present invention is included, when the compounding amount is outside the scope of the present invention (Comparative Examples 13 to 18), the resistance to nail scratches at the initial stage and after wiping off the solvent is inferior. or the extrudability was inferior.

Claims (6)

(A) Per 100 parts by mass of polycarbonate resin, (B) contains 0.3 to 10.0 parts by mass of diester compound,
The (A) polycarbonate resin contains 5 mol% or more of structural units represented by the following formula (1) among all structural units,
The diester compound (B) is a diester compound obtained from a dihydric carboxylic acid and a monohydric alcohol having 16 or more carbon atoms, or a diester compound obtained from a dihydric alcohol and a monohydric carboxylic acid having 16 or more carbon atoms. , or a mixture thereof,
resin composition;
formula (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, X ¹ represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group. The (B) diester compound is a diester compound obtained from a dihydric carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 16 to 30 carbon atoms, or a dihydric alcohol having 3 to 10 carbon atoms and 16 to 16 carbon atoms. 4. The resin composition according to claim 1, which is a diester compound obtained from 40 monovalent carboxylic acids, or a mixture thereof. The resin composition according to claim 1 or 2 , wherein the (A) polycarbonate resin further comprises a structural unit represented by the following formula (2);
formula (2)

In formula (2), X ² represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group. The (A) polycarbonate resin contains 5 to 95 mol% of the structural unit represented by the formula (1) and 95 to 5 mol% of the structural unit represented by the formula (2) in all structural units. The resin composition according to claim 3 . 5. The resin composition according to any one of claims 1 to 4 , which has a haze of 5.0% or less when molded into a molded article having a thickness of 2 mm. A molded article formed from the resin composition according to any one of claims 1 to 5 .